Abstract
With outer space being speculated as the source of handedness in molecules of biological importance, there is a great need to explore the gas-phase stereoinversion in molecules under the conditions akin to interstellar medium. In this work, quantum-mechanical computations are performed to trace the pathways for gas-phase stereoinversion in isoleucine, an amino acid with two chiral centres. Contrary to the previous such work on a two-chiral centre proteinogenic amino acid, threonine, the present work could not trace a complete stereoinversion pathway on the potential energy surface of isoleucine. The failure in case of isoleucine is attributed to its branched aliphatic side chain which hindered a complete inversion in isoleucine. However, the diastereomeric conversion pathways explored in this work for isoleucine support the distribution of different stereoisomers reported in the meteoritic composition. Notably, this study also revealed that the chirality of the aldehydic precursors may hold the key to enantio-biasing observed for isoleucine in the meteoritic samples.
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Abplanalp, M.J., Gozem, S., Krylov, A.I., Shingledecker, C.N., Herbst, E., Kaiser, R.I.: A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules. Proc. Natl. Acad. Sci. 113, 7727–7732 (2016). https://doi.org/10.1073/pnas.1604426113
Bada, J.L., Zhao, M., Steinberg, S., Ruth, E.: Isoleucine stereoisomers on the Earth. Nature 319, 314–316 (1986)
Becke, A.D.: Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993). https://doi.org/10.1063/1.464913
Burton, A.S., Stern, J.C., Elsila, J.E., Glavin, D.P., Dworkin, J.P.: Understanding prebiotic chemistry through the analysis of extraterrestrial amino acids and nucleobases in meteorites. Chem. Soc. Rev. 41, 5459–5472 (2012). https://doi.org/10.1039/c2cs35109a
Chen, Y.J., Nuevo, M., Yih, T.S., Ip, W.H., Fung, H.S., Cheng, C.Y., Tsai, H.R., Wu, C.Y.R.: Amino acids produced from the ultraviolet/extreme-ultraviolet irradiation of naphthalene in a H2O+NH3 ice mixture. Mon. Not. R. Astron. Soc. 384, 605–610 (2008). https://doi.org/10.1111/j.1365-2966.2007.12687.x
Cronin, J.R., Pizzarello, S.: Amino acids in meteorites. Adv. Space Res. 3, 5–18 (1983). https://doi.org/10.1016/0273-1177(83)90036-4
Hörst, S.M., Yelle, R.V., Buch, A., Carrasco, N., Cernogora, G., Dutuit, O., Quirico, E., Sciamma-O’Brien, E., Smith, M.A., Somogyi, A., Szopa, C., Thissen, R., Vuitton, V.: Formation of amino acids and nucleotide bases in a titan atmosphere simulation experiment. Astrobiology 12, 809–817 (2012). https://doi.org/10.1089/ast.2011.0623
Kaur, R., Vikas: Mechanisms for the inversion of chirality: global reaction route mapping of stereochemical pathways in a probable chiral extraterrestrial molecule, 2-aminopropionitrile. J. Chem. Phys. 142, 074307 (2015). https://doi.org/10.1063/1.4907593
Kaur, R., Rani, N., Vikas: Gas-phase stereoinversion in aspartic acid: reaction pathways, computational spectroscopic analysis, and its astrophysical relevance. ACS Omega 3, 14431–14447 (2018). https://doi.org/10.1021/acsomega.8b01721
Koga, T., Naraoka, H.: A new family of extraterrestrial amino acids in the Murchison meteorite. Sci. Rep. 7, 636 (2017). https://doi.org/10.1038/s41598-017-00693-9
Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A., Krishnan, R., Binkley, J.S., Seeger, R., Pople, J.A.: A self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J. Chem. Phys. 72, 650–654 (1980). https://doi.org/10.1063/1.438955
Lee, C., Yang, W., Parr, R.G.: Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 37, 785–789 (1988). https://doi.org/10.1103/PhysRevB.37.785
Lesarri, A., Sa, R., Cocinero, E.J., Lo, J.C., Alonso, L.: Coded Amino Acids in Gas Phase: the Shape of Isoleucine. J. Am. Chem. Soc., 12952–12956 (2005). https://doi.org/10.1021/ja0528073
Maeda, S., Ohno, K.: No activation barrier synthetic route of glycine from simple molecules (NH3, CH2, and CO2) via carboxylation of ammonium ylide: a theoretical study by the scaled hypersphere search method. Chem. Phys. Lett. 398, 240–244 (2004). https://doi.org/10.1016/j.cplett.2004.09.062
Maeda, S., Ohno, K., Morokuma, K.: Systematic exploration of the mechanism of chemical reactions: the global reaction route mapping (GRRM) strategy using the ADDF and AFIR methods. Phys. Chem. Chem. Phys. 15, 3683–3701 (2013). https://doi.org/10.1039/c3cp44063j
De Marcellus, P., Meinert, C., Myrgorodska, I., Nahon, L., Buhse, T.: Aldehydes and sugars from evolved precometary ice analogs: importance of ices in astrochemical and prebiotic evolution. Proc. Natl. Acad. Sci. 112, 965–970 (2014). https://doi.org/10.1073/pnas.1418602112
De Marcellus, P., Meinert, C., Myrgorodska, I., Nahon, L., Buhse, T., D’Hendecourt, L.L.S., Meierhenrich, U.J.: Aldehydes and sugars from evolved precometary ice analogs: importance of ices in astrochemical and prebiotic evolution. Proc. Natl. Acad. Sci. USA 112, 956–970 (2015). https://doi.org/10.1073/pnas.1418602112
McGuire, B.A.: Census of interstellar, circumstellar, extragalactic, protoplanetary disk, and exoplanetary molecules. Astrophys. J. Suppl. Ser. 239, 17 (2018). https://doi.org/10.3847/1538-4365/aae5d2. 2018
Mcguire, B.A., Carroll, P.B., Loomis, R.A., Finneran, I.A., Jewell, P.R., Remijan, A.J., Blake, G.A.: Discovery of the interstellar chiral molecule propylene oxide (CH3CHCH2O). Science 352, 1449–1455 (2016)
Monroe, A.A., Pizzarello, S.: The soluble organic compounds of the Bells meteorite: not a unique or unusual composition. Geochim. Cosmochim. Acta 75, 7585–7595 (2011). https://doi.org/10.1016/j.gca.2011.09.041
Nelson, D.L., Cox, M.M., Lehninger, A.L.: Principles of Biochemistry. Worth Publishers, New York (2005)
Nuevo, M., Auger, G., Blanot, D., D’Hendecourt, L.: A detailed study of the amino acids produced from the vacuum UV irradiation of interstellar ice analogs. Orig. Life Evol. Biosph. 38, 37–56 (2008). https://doi.org/10.1007/s11084-007-9117-y
Ohno, K., Maeda, S.: Global reaction route mapping on potential energy surfaces of formaldehyde, formic acid and their metal-substituted analogues. J. Phys. Chem. A 110, 8933–8941 (2006a). https://doi.org/10.1016/j.cplett.2007.09.002
Ohno, K., Maeda, S.: D-L conversion pathways between optical isomers of alanine: applications of the scaled hypersphere search method to explore unknown reaction routes in a chiral system. Chem. Lett. 35, 492–493 (2006b). https://doi.org/10.1246/cl.2006.492.
Parker, E.T., Cleaves, H.J., Dworkin, J.P., Glavin, D.P., Callahan, M., Aubrey, A., Lazcano, A., Bada, J.L.: Primordial synthesis of amines and amino acids in a 1958 Miller H2S-rich spark discharge experiment. Proc. Natl. Acad. Sci. USA 108, 5526–5531 (2011). https://doi.org/10.1073/pnas.1019191108
Pizzarello, S.: Identifying chiral molecules and their enantiomeric excesses in extraterrestrial samples: an experimental journey. Isr. J. Chem. 56, 1027–1035 (2016a). https://doi.org/10.1002/ijch.201600039
Pizzarello, S.: Molecular asymmetry in prebiotic chemistry: an account from meteorites. Life 6, 18 (2016b). https://doi.org/10.3390/life6020018
Pizzarello, S., Cronin, J.R.: Non-racemic amino acids in the Murray and Murchison meteorites. Geochim. Cosmochim. Acta 64, 329–338 (2000). https://doi.org/10.1016/S0016-7037(99)00280-X
Pizzarello, S., Holmes, W.: Nitrogen-containing compounds in two CR2 meteorites: 15N composition, molecular distribution and precursor molecules. Geochim. Cosmochim. Acta 73, 2150–2162 (2009). https://doi.org/10.1016/j.gca.2009.01.022
Pizzarello, S., Shock, E.: The organic composition of carbonaceous meteorites: the evolutionary story ahead of biochemistry. Cold Spring Harb. Perspect. Biol. 2, a002105 (2010). https://doi.org/10.1101/cshperspect.a002105
Pizzarello, S., Huang, Y., Alexandre, M.R.: Molecular asymmetry in extraterrestrial chemistry: insights from a pristine meteorite. Proc. Natl. Acad. Sci. 105, 3700–3704 (2008). https://doi.org/10.1073/pnas.0709909105
Rani, N., Vikas: Mechanism and kinetics of the gas-phase stereoinversion in proteinogenic \(L\)-threonine and its astrophysical relevance. J. Phys. Chem. A 122, 7572–7586 (2018). https://doi.org/10.1021/acs.jpca.8b06659
Rani, N., Vikas: Mechanism and kinetics of astrophysically relevant gas-phase stereoinversion in glutamic acid: a computational study. Mol. Astrophys. 18, 100061 (2020a). https://doi.org/10.1016/j.molap.2019.100061
Rani, N., Vikas: Extra-terrestrial gas-phase stereoinversion in amino acid leucine: thermal and photochemical channels. ChemPhysChem 21, 1107–1118 (2020b). https://doi.org/10.1002/cphc.202000230
Ring, D., Wolman, Y., Friedmann, N., Miller, S.L.: Prebiotic synthesis of hydrophobic and protein amino acids. Proc. Natl. Acad. Sci. USA 69, 765–768 (1972). https://doi.org/10.1073/pnas.69.3.765
Shimoyama, A., Harada, K., Yaani, K.: Amino acids from the Yamato-791198 Carbonaceous Chondrite from Antarctica. Chem. Lett. 14, 1183–1186 (1985)
Stepanian, S.G., Yu, A., Adamowicz, L.: Conformational composition of neutral leucine. Matrix isolation infrared and ab initio study. Chem. Phys. 423, 20–29 (2013). https://doi.org/10.1016/j.chemphys.2013.06.018
Strecker, A.: Ueber einen neuen aus Aldehyd-Ammoniak und Blausäure entstehenden Körrper. Ann. Chem. Pharm. 91, 349–351 (1854). https://doi.org/10.1017/CBO9781107415324.004
Acknowledgements
Namrata Rani thanks University Grants Commission (UGC), New Delhi (India), for providing SRF(NET) fellowship. The authors are also grateful to the Department of Chemistry, Panjab University, Chandigarh, for providing other computational software and other resources.
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Financial assistance from Science & Engineering Research Board (SERB), India, under a research project (sanction order No. EMR/2016/002074) is gratefully acknowledged.
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Rani, N., Vikas Gas-phase stereoinversion in proteinogenic amino acid isoleucine: its astrophysical importance. Astrophys Space Sci 366, 38 (2021). https://doi.org/10.1007/s10509-021-03940-8
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DOI: https://doi.org/10.1007/s10509-021-03940-8